Temporary bonding laminates for use in manufacture of semiconductor devices and method for manufacturing semiconductor devices

ABSTRACT

A temporary bonding laminate for use in the manufacture of semiconductor devices and a method for manufacturing semiconductor devices are provided. A member to be processed (a semiconductor wafer or the like) can be temporarily supported securely and readily during a mechanical or chemical process of the member, and then the processed member can be readily released from the temporary support without damaging the processed member even after a high temperature process. The laminate includes: (A) a release layer and (B) an adhesive layer. The release layer contains (a1) a compound being liquid at 25° C. and having a 5% mass reduction temperature of 250° C. or more when measured in a nitrogen gas stream under heating conditions of a constant heating rate of 20° C./min; and (a2) a binder having a 5% mass reduction temperature of 250° C. or more when measured under the same conditions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2014/058325 filed on Mar. 25, 2014, which claims priority under 35U.S.C § 119(a) to Japanese Patent Application No. 2013-064435 filed onMar. 26, 2013. Each of the above application(s) is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

TECHNICAL FIELD

The present invention relates to temporary bonding laminates for used ina manufacture of semiconductor devices and method for manufacturingsemiconductor devices.

BACKGROUND ART

Conventional manufacturing processes of semiconductor devices such asICs and LSIs typically comprise forming a number of IC chips on asemiconductor silicon wafer and singulating it by dicing.

The demand for smaller electronic equipment with higher performance alsoleads to a demand for smaller IC chips with a higher degree ofintegration incorporated into the electronic equipment, but the densityof integrated circuits in the direction of the plane of siliconsubstrates is close to the limit.

Wire bonding is a conventionally widely known technique for electricallyconnecting integrated circuits in IC chips to external terminals of theIC chips, and an alternative technique suitable for smaller IC chips hasalso recently been known, which comprises forming through-holes in asilicon substrate and connecting metal plugs as external terminals tointegrated circuits via the through-holes (so-called, a method forforming a through-silicon electrode (TSV)). However, the techniquecomprising forming through-silicon vias alone cannot sufficiently meetthe recent demand for IC chips with a higher degree of integration.

To overcome the drawbacks described above, a technique is known forimproving the degree of integration per unit area of silicon substratesby providing multilayer integrated circuits in IC chips. However, themultilayer integrated circuits increase the thickness of the IC chips sothat components of the IC chips must be thinned. Such componentssuggested to be thinned include, for example, silicon substrates, andthis is a promising solution because it allows not only for reducing thesize of IC chips but also for saving labor in the step of formingthrough-holes in silicon substrates during the preparation ofthrough-silicon vias.

The semiconductor silicon wafer used in a method for manufacturingsemiconductor device are widely known to have a thickness of about 700to 900 μm. Recently, for the purpose of miniaturization or the like ofan IC chip, the semiconductor silicon wafer has been attempted to reducethe thickness of the semiconductor silicon wafer to be 200 μm or less.To reduce the size of IC chips or for other purposes, attempts haverecently been made to reduce the thickness of semiconductor siliconwafers to be 200 μm or less.

However, semiconductor silicon wafers having a thickness of 200 μm orless are so thin and therefore, components for manufacturingsemiconductor devices using them as base materials are also so thin thatsuch components are hard to stably support without damaging them duringfurther processing or simply transferring or otherwise handling suchcomponents.

To solve the problems as described above, a known technique comprisestemporarily bonding an unthinned semiconductor wafer having devices onits surface to a supporting substrate for processing using a siliconeadhesive; thinning the semiconductor wafer by backgrinding; thendrilling the semiconductor wafer to form through-silicon vias; and thendebonding the supporting substrate for processing from the semiconductorwafer (see patent document 1). It is said that this technique allows forachieving resistance to grinding during backgrinding of thesemiconductor wafer, heat resistance during an anisotropic dry etchingprocess or the like, chemical resistance during plating or etching,smooth separation from the supporting substrate for processing at thefinal stage and low contamination on the wafer at the same time.

A technique for supporting a wafer by a carrier layer system is alsoknown, comprising inserting a plasma polymer layer obtained by plasmadeposition as a separation layer between the wafer and the carrier layersystem in such a manner that the bond strength between the carrier layersystem and the separation layer is greater than the bond strengthbetween the wafer and the separation layer, whereby the wafer is readilydebonded from the separation layer when the wafer is debonded from thecarrier layer system (see patent document 2).

Another known technique comprises a temporary bonding step using apolyether sulfone and a tackifier, and a debonding step by heating(patent document 3).

Another known technique comprises a temporary bonding step using amixture of a carboxylic acid and an amine, and a debonding step byheating (patent document 4).

Another known technique comprises bonding a device wafer and a carriersubstrate under pressure via a heated bonding layer formed of acellulose polymer or the like, and debonding the device wafer from thecarrier substrate by heating and sliding apart them in a transversedirection (patent document 5).

Further, an adhesive film comprising syndiotactic 1,2-polybutadiene anda photoinitiator is known, wherein the bond strength of the film can bechanged by irradiation (patent document 6).

Another known technique comprises temporarily bonding a carriersubstrate and a semiconductor wafer using an adhesive formed of apolycarbonate, processing the semiconductor wafer, then irradiating it,and then debonding the processed semiconductor wafer from the carriersubstrate by heating (patent document 7).

Further, a known technique for temporarily bonding a device surface of adevice wafer having microdevices and a carrier substrate supporting thedevice wafer comprises temporarily bonding a peripheral region of thedevice surface and the carrier substrate with an adhesive via a filllayer not participating in bonding inserted between a central region ofthe device surface and the carrier substrate (patent document 8).

REFERENCES Patent Documents

Patent document 1: JPA2011-119427;

Patent document 2: JPA2009-528688;

Patent document 3: JPA2011-225814;

Patent document 4: JPA2011-052142;

Patent document 5: JPA2010-506406;

Patent document 6: JPA2007-045939;

Patent document 7: US Patent Application Publication No. 2011/0318938;

Patent document 8: JPA2011-510518.

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

When a surface of a semiconductor wafer having devices (i.e., a devicesurface of a device wafer) and a supporting substrate (carriersubstrate) are to be temporarily bonded via a layer formed of anadhesive known from patent document 1 or the like, the adhesive layermust have enough adhesiveness to stably support the semiconductor wafer.

Thus, when the entire device surface of a semiconductor wafer and asupporting substrate are to be temporarily bonded via an adhesive layer,the following problem is likely to occur: the temporary bond between thesemiconductor wafer and the supporting substrate must be enough strongto stably support the semiconductor wafer without damaging it, but thetemporary bond between the semiconductor wafer and the supportingsubstrate is so strong that devices may be broken or separated from thesemiconductor wafer when the semiconductor wafer is debonded from thesupporting substrate.

Further, the method comprising forming a plasma polymer layer as aseparation layer by plasma deposition between a wafer and a carrierlayer system to prevent the wafer and the carrier layer system frombeing bonded too strongly as described in patent document 2 has thefollowing drawbacks: (1) the equipment for performing plasma depositiontypically requires much cost; (2) the layer formation by plasmadeposition requires a considerable time for evacuation in a plasmadeposition system or deposition of a monomer; and (3) even if aseparation layer formed of a plasma polymer layer is inserted, it is noteasy to control the bond strength in such a manner that the bondstrength between the wafer and the separation layer is enough when thewafer to be processed is supported, while the wafer is readily debondedfrom the separation layer when the wafer is released from the support.

Further, the method comprising a debonding step by heating as describedin patent documents 3, 4 and 5 is likely to encounter the problem thatdevices may be broken by lengthy heating.

Further, the method comprising a debonding step by irradiation asdescribed in patent documents 6 and 7 necessitates the use of aradiation-transparent carrier substrate.

Further, the method comprising inserting a fill layer not participatingin bonding on a carrier as described in patent document 8 must comprisea multistage process for forming the fill layer, and therefore it shouldbe further improved in productivity.

The present invention was made under the circumstances described above,and aims to provide temporary bonding laminates for used in amanufacture of semiconductor devices, by which a member to be processed(a semiconductor wafer or the like) can be temporarily supportedsecurely and readily during a mechanical or chemical process of themember to be processed and then the processed member can be readilyreleased from the temporary support without damaging the processedmember even after a high temperature process, and method formanufacturing semiconductor devices. Father, to provide temporarybonding laminates for used in a manufacture of semiconductor deviceswith high anti-outgassing performance, and method for manufacturingsemiconductor devices using such laminates.

Means for Solving the Problems

As a result of our careful studies to solve the problems describedabove, we achieved the present invention on the basis of the findingthat if a temporary bonding laminate comprising a release layer and anadhesive layer is provided between a support and a member to beprocessed wherein the release layer comprises (a1) a compound beingliquid at 25° C. and having a 5% mass reduction temperature of 250° C.or more when measured in a nitrogen gas stream under heating conditionsof a constant heating rate of 20° C./min, and (a2) a binder having a 5%mass reduction temperature of 250° C. or more when measured in anitrogen gas stream under the heating conditions of a constant heatingrate of 20° C./min, the permeation of stripping solvents into therelease layer is promoted whereby the processed member can be readilyreleased from the temporary support even after a high temperatureprocess and outgassing can also be reduced.

Specifically, the problems were solved by the solving means <1>,preferably by solving means <2> to <13> below.

<1> A temporary bonding laminate for used in a manufacture ofsemiconductor devices, comprising: (A) a release layer and (B) anadhesive layer,

wherein the release layer comprises (a1) a compound being liquid at 25°C. and having a 5% mass reduction temperature of 250° C. or more whenmeasured in a nitrogen gas stream under heating conditions of a constantheating rate of 20° C./min; and (a2) a binder having a 5% mass reductiontemperature of 250° C. or more when measured in a nitrogen gas streamunder heating conditions of a constant heating rate of 20° C./min.

<2> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to <1>, wherein the release layer (A)has a softening point of 200° C. to 450° C.

<3> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to <1> or <2>, wherein the binder (a2)is a thermoplastic resin.

<4> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to <3>, wherein the thermoplastic resinis at least one kind of thermoplastic resin selected from polyethersulfone resins, polyimide resins, polyester resins, polybenzimidazoleresins, polyphenylene ether resins, polyphenylene sulfide resins,polyamide-imide resins and polyether ketone resins.<5> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to any one of <1> to <4>, wherein theliquid compound (a1) is selected from polyol esters, diesters,polyphenyl ethers, organopolysiloxanes, polyethylene glycols,polypropylene glycols, long-chain carboxylic acids and ionic liquids.<6> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to any one of <1> to <5>, wherein theliquid compound (a1) is contained in an amount of 0.01 to 10% by mass ofthe release layer.<7> The temporary bonding laminate for used in a manufacture ofsemiconductor devices according to any one of <1> to <6>, wherein theadhesive layer (B) comprises a binder, a polymerizable monomer, and atleast one of a photoinitiator and a thermal polymerization initiator.<8> A method for manufacturing a semiconductor device, comprising:

bonding a first surface of a member to be processed and a substrate viathe temporary bonding laminate for used in a manufacture ofsemiconductor devices according to any one of <1> to <7>;

subjecting the member to be processed to a heat treatment having amaximum attainable temperature in a range of 180° C. to 370° C. to givea processed member; and debonding the processed member from the bondinglayer laminate, thereby preparing a semiconductor device incorporatingthe processed member; wherein the release layer has 5% mass reductiontemperature higher than the maximum attainable temperature in the heattreatment when measured in a nitrogen gas stream under heatingconditions of a constant heating rate of 20° C./min.

<9> The method for manufacturing a semiconductor device according to<8>, further comprising irradiating the adhesive layer of the temporarybonding laminate with active rays or radiation or heat before bondingthe first surface of the member to be processed and the substrate viathe temporary bonding laminate.<10> The method for manufacturing a semiconductor device according to<8> or <9>, further comprising removing the temporary bonding laminateremaining on the processed member with a stripping solvent afterdebonding the processed member from the temporary bonding laminate.<11> The method for manufacturing a semiconductor device according to<10>, wherein the stripping solvent comprises at least one kind ofhydrocarbon solvents and ether solvents.<12> The method for manufacturing a semiconductor device according to<11>, wherein the stripping solvent comprises at least one kind ofcyclopentane, n-hexane, cyclohexane, n-heptane, limonene, p-menthane,tetrahydrofuran (THF), 1,3-dioxolane, and anisole.<13> A kit comprising a release layer forming composition and anadhesive layer forming composition,wherein the release layer forming composition contains (a1) a compoundbeing liquid at 25° C. and having 5% mass reduction temperature of 250°C. or more when measured in a nitrogen gas stream under the heatingconditions of a constant heating rate of 20° C./min, and (a2) a binderhaving 5% mass reduction temperature of 250° C. or more when measured ina nitrogen gas stream under the heating conditions of a constant heatingrate of 20° C./min.

Advantages of the Invention

The present invention makes it possible to provide temporary bondinglaminates for used in a manufacture of semiconductor devices, that allowa member to be processed to be temporarily supported securely andreadily during a mechanical or chemical process of the member to beprocessed and then the processed member to be readily released from thetemporary support without damaging the processed member even after ahigh temperature process, and also to provide method for manufacturingsemiconductor devices using such laminates. Further, temporary bondinglaminates for used in a manufacture of semiconductor devices with highanti-outgassing performance, and method for manufacturing semiconductordevices using such laminates can also be provided.

FIG. 1A is a schematic diagram showing how a solvent permeates through arelease layer according to the present invention and, FIG. 1B is aschematic diagram showing how a solvent permeates through a releaselayer according to the prior art.

FIG. 2 is a schematic diagram of a solvent shows a state of penetratingthe surface of the release layer in the present invention.

FIG. 3A, FIG. 3B and FIG. 3C are a schematic sectional view illustratinghow to temporarily bond an adhesive support and a device wafer, aschematic sectional view showing the device wafer temporarily bonded tothe adhesive support, and a schematic sectional view showing the devicewafer temporarily bonded to the adhesive support after it has beenthinned, respectively.

FIG. 4 is a schematic top view of an adhesive support according to thepresent invention.

FIG. 5 is a schematic top view of an adhesive support according to thepresent invention.

FIG. 6 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 7 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 8 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 9 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 10 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 11 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 12 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 13 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 14 is a schematic top view of an adhesive support according to anembodiment of the present invention.

FIG. 15 is a schematic sectional view illustrating how an adhesivesupport and a device wafer are released from a temporary bond accordingto a prior art.

DESCRIPTION OF EMBODIMENTS

The present invention will be explained in detail below.

In this specification, notation of group (atomic group) without beingpreceded by “substituted” or “unsubstituted”, is used to encompass notonly group having no substituent, but also group having substituent. Forexample, “alkyl group” encompass not only alkyl group having nosubstituent (unsubstituted alkyl group), but also alkyl group havingsubstituent (substituted alkyl group). In the present specification, theterm “monomer” and “monomer” is synonymous.

In this specification, “actinic rays” and “radiation” means, forexample, those with visible light, ultraviolet light, far ultravioletrays, electron beams, X-rays or the like. Further, in the presentinvention, “light”, it means actinic rays or radiation.

In this specification, “exposure”, unless otherwise indicated, exposurewith far ultraviolet rays typified by mercury lamp, ultraviolet rays,excimer laser, X-ray, EUV light or the like, and a drawing with aparticle beam such as an electron beam and ion beam.

In this specification, “(meth)acrylate” means acrylate and methacrylate,“(meth)acryl” means acryl and methacryl, “(meth)acryloyl” means acryloyland methacryloyl. The monomer in the present invention is discriminatedfrom oligomer and polymer, and means any compound having aweight-average molecular weight of 2,000 or smaller. In thisspecification, the polymerizable compound means any compound having apolymerizable functional group, and may be a monomer or polymer. Thepolymerizable functional group means any group participating apolymerization reaction.

In the embodiments described below, for the members and the likedescribed in the previously referenced drawings are simplified oromitted of explanation are denoted by the same reference numerals orcorresponding reference numerals in the figures.

The temporary bonding laminates for used in a manufacture ofsemiconductor devices according to the present invention (hereinafteralso simply referred to as “temporary bonding laminates”) comprise (A) arelease layer and (B) an adhesive layer, characterized in that therelease layer comprises (a1) a compound being liquid at 25° C. having a5% mass reduction temperature of 250° C. or more when measured in anitrogen gas stream under the heating conditions of a constant heatingrate of 20° C./min (hereinafter sometimes referred to as a “heatresistant liquid”), and (a2) a binder having a 5% mass reductiontemperature of 250° C. or more when measured in a nitrogen gas streamunder the heating conditions of a constant heating rate of 20° C./min(hereinafter sometimes referred to as a “binder”). In the presentinvention, the permeation of solvents into the release layer is promotedby incorporating the heat resistant liquid (a1) into the release layer.This concept is explained with reference to FIG. 1 and FIG. 2.

FIG. 1 is a schematic diagram showing how a solvent permeates through arelease layer according to the present invention and the prior art,wherein 1 represents a release layer and 2 represents a heat resistantliquid, respectively. Further, the straight and wavy lines witharrowheads in the figure indicate how the solvent permeates. It shouldbe noted that FIG. 1 serves Only for a better understanding of theconcept of the present invention, and the amount of the heat resistantliquid and the droplet size of the heat resistant liquid in the releaselayer are not limited to those shown in FIG. 1 (as well as the otherdrawings).

According to the present invention, the heat resistant liquid 2 existsas droplets in the release layer 1, i.e., a layer comprising a binder asa main component, as shown in FIG. 1A. When a solvent enters into therelease layer as shown by the arrow in FIG. 1A, the solvent slowlypermeates through the binder as shown by the wavy lines with arrowheads,but rapidly permeates through the droplets of the heat resistant liquid.However, the solvent slowly permeated through the conventional releaselayer because a binder existed alone in it without droplets of a heatresistant liquid, as shown in FIG. 1B. Thus, the structure of thepresent invention allows the solvent to permeate through the releaselayer readily, whereby the release layer can be separated more readily.Further, the use of the heat resistant liquid allows for the reductionof outgassing even after a high temperature process.According to an alternative embodiment of the present invention, theheat resistant liquid may exist on the surface of the release layer 1,as shown in FIG. 2. In this embodiment, the surface area of the releaselayer 1 into which the solvent enters increases. As a result, thesolvent permeates into the release layer more readily, whereby therelease layer can be separated more readily.

A temporary bonding laminate for used in a manufacture of semiconductordevices of the present invention is explained hereinafter.

The temporary bonding laminates for used in a manufacture ofsemiconductor devices according to the present invention are preferablyused in a manufacture of semiconductor devices comprising the step ofperforming a heat treatment.

The temporary bonding laminates for used in a manufacture ofsemiconductor devices according to the present invention providetemporary bonding laminates for used in a manufacture of semiconductordevices, by which a member to be processed can be temporarily supportedsecurely and readily during a mechanical or chemical process of themember to be processed and then the processed member can be readilyreleased from the temporary support without damaging the processedmember even after a high temperature process. Furthermore, even whenobtaining a process at high temperature, outgassing is less likely tooccur.

The temporary bonding laminates for used in a manufacture ofsemiconductor devices according to the present invention are preferablyused for forming through-silicon vias. The formation of through-siliconvias will be explained in detail later.

<(A) Release Layer>

The release layer according to the present invention comprises (a1) acompound being liquid at 25° C. and having a 5% mass reductiontemperature (hereinafter sometimes referred to as “Td”) of 250° C. ormore when measured in a nitrogen gas stream under the heating conditionsof a constant heating rate of 20° C./min, and (a2) a binder having a 5%mass reduction temperature of 250° C. or more when measured in anitrogen gas stream under the heating conditions of a constant heatingrate of 20° C./min.

The release layer is used for the purpose of improving releasability.Therefore, the release layer should have releasability less influencedby heat. Bearing in mind the temperature at which semiconductor elementsare typically processed, the release layer preferably has a softeningpoint of 200° C. to 450° C., more preferably 250° C. to 400° C., evenmore preferably 280° C. to 350° C. In this connection, the softeningpoint of the release layer refers to the value measured by aconventional method using a viscoelastometer.

This seems to prevent the resin in the release layer from being moltenor undergoing a glass transition by heat during manufacturing processesof semiconductor devices comprising performing a heat treatment andthereby from being bonded to the adhesive layer to an excessive degree,with the result that the processed member is smoothly separated.

The softening point of the release layer is determined as thetemperature at which the loss tangent (tan δ) measured using aviscoelastometer under predetermined heating conditions is maximum.

The loss tangent (tan δ) is calculated by the equation below:tan δ=G″/G′

wherein G″ represents shear loss modulus, and G′ represents shearstorage modulus.

The heating rate is preferably in the range of 0.5 to 20° C./min, morepreferably in the range of 1 to 10° C./min, especially preferably in therange of 2 to 5° C./min.

The heat resistant liquid and the binder that the release layer of thepresent invention comprises are explained in detail below.

<<Heat Resistant Liquid>>

In the present invention, any compound that is liquid at ambienttemperature and has a Td of 250° C. or more can be used as the heatresistant liquid contained in the release layer composition.

Heat resistant liquids include, for example, polyol esters, diesters,polyphenyl ethers, organopolysiloxanes, polyethylene glycols,polypropylene glycols, long-chain carboxylic acids, ionic liquids andthe like. Among them, preferred are polyol esters, organopolysiloxanes,and ionic liquids, more preferably polyol esters and ionic liquids,especially preferably polyol esters.

Specifically, UNISTER H481R (a polyester polyol having a Td of 260° C.from NOF CORPORATION), KF-54 (a polyorganosiloxane having a Td of 270°C. from Shin-Etsu Chemical Co., Ltd.), and an ionic liquid (an ionicliquid having a Td of 310° C. from Nisshinbo) can be used.

The heat resistant liquid is used for the purpose of improving theremoval of the release layer with a stripping solvent. As describedabove, the incorporation of the heat resistant liquid into the releaselayer composition allows small droplets to be generated in the releaselayer, thereby improving the permeation of solvents into the releaselayer. Typical manufacturing processes of semiconductors involve heatinga member to be processed at a high temperature of 200° C. or more. Theseheating steps are associated with the problem of outgassing, i.e., a gasof some substance is released from the processed member to contaminatethe equipment. In the present invention, outgassing can be effectivelyreduced because a heat resistant liquid having a Td of 250° C. or moreis used. Thus, the heat resistant liquid used in the present inventionpreferably has a Td of 270° C. or more, especially preferably 300° C. ormore.

If desired, multiple heat resistant liquids may be used in combination.

The amount of the heat resistant liquid contained in the release layerof the present invention is preferably 0.01 to 10% by mass, morepreferably 0.1 to 5% by mass, especially preferably 0.5 to 1% by mass ofthe release layer of the present invention. When it is in such ranges,the advantages of the present invention are achieved more effectively.

<<Binder>>

In the present invention, any binders can be used as the bindercontained in the above release layer.

For example, they include synthetic resins such as terpene resins,terpene phenol resins, modified terpene resins, hydrogenated terpeneresins, hydrogenated terpene phenol resins, rosins, rosin esters,hydrogenated rosins, hydrogenated rosin esters, polymerized rosins,polymerized rosin esters, modified rosins, rosin-modified phenolicresins, alkyl phenolic resins, aliphatic petroleum resins, aromaticpetroleum resins, hydrogenated petroleum resins, modified petroleumresins, alicyclic petroleum resins, coumarone petroleum resins, indenepetroleum resins, olefin copolymers (e.g., methylpentene copolymers),cycloolefin copolymers (e.g., norbornene copolymers, dicyclopentadienecopolymers, tetracyclododecene copolymers), novolac resins, phenolicresins, epoxy resins, melamine resins, urea resins, unsaturatedpolyester resins, alkyd resins, polyurethane resins, polyimide resins,polyethylene resins, polypropylene resins, polyvinyl chloride resins,polystyrene resins, polyvinyl acetate resins, PTFE resins, PFA resins,FEP resins, ethylene-TFE copolymer resins, PVDF resins, PCTFE resins,ethylene-CTFE resins, TFE-perfluorodimethyldioxole copolymer resins, PVFresins, ABS resins, AS resins, acrylic resins, cellulose resins,polyamides, polyacetals, polycarbonates, polyphenylene ethers,polybutylene terephthalates, polyethylene terephthalates, cyclicpolyolefins, polyphenylene sulfides, polysulfones, polyether sulfoneresins, polybenzimidazole resins, polyarylate resins, polyether ketoneresins, and polyamideimide resins; and natural resins such as naturalrubbers. Among others, preferred are PTFE resins, PFA resins, FEPresins, ethylene-TFE copolymer resins, PVDF resins, PCTFE resins,ethylene-CTFE resins, TFE-perfluorodimethyldioxole copolymer resins, PVFresins, polyether sulfone resins, polyimide resins, polyester resins,polybenzimidazole resins, polyphenylene ether resins, polyamideimideresins, and polyether ketone resins, more preferably PFA resins,TFE-perfluorodimethyldioxole copolymer resins, PVF resins, polyethersulfone resins, polyimide resins, polyester resins, polybenzimidazoleresins, polyphenylene ether resins, polyamideimide resins, and polyetherketone resins, especially preferably polyether sulfone resins, polyimideresins, polyester resins, polybenzimidazole resins, polyamideimideresins, polyphenylene ether resins, and polyether ketone resins.

Preferably, the binder is a thermoplastic resin, especially preferablyat least one kind of thermoplastic resin selected from polyether sulfoneresins, polyimide resins, polyester resins, polybenzimidazole resins,polyphenylene ether resins, polyamideimide resins and polyether ketoneresins.

Preferably, the binder used in the present invention has a Td of 270° C.or more, especially preferably 300° C. or more.

If desired, multiple binders may be used in combination.

The amount of the binder contained in the release layer of the presentinvention is preferably 1 to 100% by mass, more preferably 70 to 100% bymass, especially preferably 90 to 100% by mass based on the total solids(i.e., the amount excluding the solvent) of the release layer of thepresent invention.

<<Solvent>>

In the present invention, a solvent is typically used to form therelease layer. Any known solvents that can form the release layer can beused without limitation, including N-methyl-2-pyrrolidone,N,N-dimethylacetamide, 2-butanone, methyl amyl ketone, anisole, xyleneand the like, preferably N-methyl-2-pyrrolidone, N,N-dimethylacetamide,methyl amyl ketone or anisole.

The solvents are preferably used in such an amount that the solidscontent of the release layer composition for forming the first releaselayer is 5 to 40% by mass.

<<Other Additives>>

The release layer may optionally contain various additives.

The release layer composition of the present invention may containvarious surfactants to further improve coatability. Surfactants that canbe used include various surfactants such as fluorosurfactant, nonionicsurfactants, cationic surfactants, anionic surfactants, siliconesurfactants and the like.

Especially when the release layer composition of the present inventionused for the release layer contains a fluorosurfactant, the liquidproperties (especially flowability) of the coating solution preparedtherefrom are further improved so that the uniformity of the coatingthickness and coating consumption reduction can be further improved.

In other words, when a coating solution prepared from the release layercomposition containing a fluorosurfactant is used to form a film,interfacial tension between the substrate surface and the coatingsolution decreases, whereby wettability on the substrate surface andcoatability on the substrate surface are improved. Thus, suchembodiments are effective because a film of an even and uniformthickness can be formed more suitably even if it is formed in a smallthickness in the order of several micrometers by using a small amount ofthe coating solution.

The fluorine content in the fluorosurfactant is preferably 3% by mass to40% by mass, more preferably 5% by mass to 30% by mass, especiallypreferably 7% by mass to 25% by mass. Fluorosurfactants having afluorine content in the ranges indicated above are effective forobtaining coated films having a uniform thickness and for reducingcoating consumption, and they are also well soluble in the release layercomposition.

Fluorosurfactants include, for example, Megaface F171, F172, F173, F176,F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780,and F781 (all from DIC Corporation); Fluorad FC430, FC431, and FC171(all from Sumitomo 3M Limited); SURFLON S-382, SC-101, SC-103, SC-104,SC-105, SC1068, SC-381, SC-383, 5393, and KH-40 (all from ASAHI GLASSCO., LTD.); PF636, PF656, PF6320, PF6520, and PF7002 (from OMNOVA) andthe like.

Nonionic surfactants specifically include glycerol, trimethylolpropane,trimethylolethane as well as ethoxylates and propoxylates thereof (e.g.,glycerol propoxylate, glycerol ethoxylate and the like); polyoxyethylenelauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleylether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenylether, polyethylene glycol dilaurate, polyethylene glycol distearate,sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2 and25R2, and Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF;Solsperse 20000 from Lubrizol Japan Limited) and the like.

Cationic surfactants specifically include phthalocyanine derivatives(available from Morishita Sangyo K.K. under the brand name EFKA-745);the organosiloxane polymer KP341 (from Shin-Etsu Chemical Co., Ltd.);the (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, and No. 95 (fromKyoeisha Chemical Co., Ltd.); W001 (from Yusho Co., Ltd.); and the like.

Anionic surfactants specifically include W004, W005 and W017 (from YushoCo., Ltd.) and the like.

Silicone surfactants include, for example, “Toray Silicone DC3PA”,“Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray SiliconeSH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA”, “ToraySilicone SH30PA”, and “Toray Silicone SH8400” from Dow Corning TorayCo., Ltd.; “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, and“TSF-4452” from Momentive Performance Materials Inc.; “KP341”, “KF6001”,and “KF6002” from Shin-Etsu Silicone, Co., Ltd.; “BYK307”, “BYK323”, and“BYK330” from BYK Japan KK; and the like.

The surfactants may be used alone or as a combination of two or more ofthem.

The amount of the surfactants to be added is preferably 0.001% by massto 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass based onthe total solids of the release layer composition.

The method for forming the release layer of the temporary bondinglaminates for used in a manufacture of semiconductor devices accordingto the present invention is not specifically limited, but can besuitably accomplished by appropriately changing the types and amounts ofbinders described above as preferred examples, i.e., by using a binderselected from the preferred specific examples indicated above at a morepreferred concentration.

<(B) Adhesive Layer>

The adhesive layer is used for the purpose of bonding the release layerand the substrate. Therefore, the adhesive layer should haveadhesiveness less influenced by heat/chemicals.

The adhesive layer can be formed by applying (preferably coating) anadhesive composition containing various components described later on acarrier substrate using a known technique such as spin coating, spraycoating, roller coating, flow coating, blade coating, dip coating or thelike, and then drying it.

Further, the adhesive layer may be a layer having an adhesiveness thatincreases or decreases by irradiation with active rays or radiation or alayer having two or more regions of different bond strengths obtained byexposing the surface of a layer having an adhesiveness that increases ordecreases by irradiation with active rays or radiation.

Exposure is preferably pattern exposure using a mask, specifically asdescribed later.

The thickness of the adhesive layer is, for example, in the range of 1to 500 μm, but not specifically limited.

<<Binder>>

Preferably, the adhesive composition (therefore, the adhesive layer)contains a binder.

In the present invention, any binders can be used. For example, theyinclude synthetic resins such as hydrocarbon resins, novolac resins,phenolic resins, epoxy resins, melamine resins, urea resins, unsaturatedpolyester resins, alkyd resins, polyurethanes, polyimides,polyethylenes, polypropylenes, polyvinyl chlorides, polystyrenes,styrene-methyl methacrylate copolymer resins, polyvinyl acetates,Teflons (registered trademark), ABS resins, AS resins, acrylic resins,polyamides, polyacetals, polycarbonates, polyphenylene ethers,polybutylene terephthalates, polyethylene terephthalates, cyclicpolyolefins, polyphenylene sulfides, polysulfones, polyether sulfones,polyarylates, polyether ether ketones, and polyamideimides; and naturalresins such as natural rubbers. Among others, preferred arepolyurethanes, novolac resins, polyimides, polystyrenes, andstyrene-methyl methacrylate copolymer resins, more preferably novolacresins, polyimides, polystyrenes, and styrene-methyl methacrylatecopolymer resins, especially preferably polyimides, polystyrenes, andstyrene-methyl methacrylate copolymer resins.

The binder may be used alone or as a combination of two or more.

In the present invention, any hydrocarbon resins can be used.

As used herein, the hydrocarbon resin basically refers to a resin solelyconsisting of carbon atoms and hydrogen atoms, but it may contain otheratoms in the side chain so far as its basic skeleton is a hydrocarbonresin. Further, the hydrocarbon resin as used herein does not include aresin in which a non-hydrocarbon functional group is directly attachedto the main chain, such as acrylic resins, polyvinyl alcohol resins,polyvinyl acetal resins, and polyvinyl pyrrolidone resins.

Hydrocarbon resins satisfying the criteria described above include, forexample, polystyrene resins, terpene resins, terpene phenol resins,modified terpene resins, hydrogenated terpene resins, hydrogenatedterpene phenol resins, rosins, rosin esters, hydrogenated rosins,hydrogenated rosin esters, polymerized rosins, polymerized rosin esters,modified rosins, rosin-modified phenolic resins, alkyl phenolic resins,aliphatic petroleum resins, aromatic petroleum resins, hydrogenatedpetroleum resins, modified petroleum resins, alicyclic petroleum resins,coumarone petroleum resins, indene petroleum resins, olefin polymers(e.g., methylpentene copolymers), cycloolefin polymers (e.g., norbornenecopolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers)and the like.

Among others, preferred are polystyrene resins, terpene resins, rosins,petroleum resins, hydrogenated rosins, polymerized rosins, olefinpolymers, and cycloolefin polymers, more preferably polystyrene resins,terpene resins, rosins, olefin polymers, and cycloolefin polymers, evenmore preferably polystyrene resins, terpene resins, rosins, olefinpolymers, polystyrene resins, and cycloolefin polymers, especiallypreferably polystyrene resins, terpene resins, rosins, cycloolefinpolymers, and olefin polymers, most preferably polystyrene resins orcycloolefin polymers.

Examples of cyclic olefin resins used for preparing cycloolefincopolymers include norbornene polymers, monocyclic olefin polymers,cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers,and hydrides of these polymers and the like. Preferred examples includeaddition (co)polymerized cyclic olefin resins containing at least one ormore repeat units represented by formula (II) below, and those addition(co)polymerized cyclic olefin resins further containing at least one ormore repeat units represented by formula (I) as appropriate. Further,other preferred examples include ring-opened (co)polymers containing atleast one cyclic repeat unit represented by formula (III).

In the formulae above, m represents an integer of 0 to 4. R¹ to R⁶ eachindependently represent a hydrogen atom or a hydrocarbon groupcontaining 1 to 10 carbon atoms, and X¹ to X³ and Y¹ to Y³ eachindependently represent a hydrogen atom, a hydrocarbon group containing1 to 10 carbon atoms, a halogen atom, a hydrocarbon group containing 1to 10 carbon atoms substituted by a halogen atom, —(CH₂)nCOOR¹¹,—(CH₂)nOCOR¹², —(CH₂) nNCO, —(CH₂)nNO₂, —(CH₂)nCN, (CH₂) nCONR¹³R¹⁴,—(CH₂) nNR¹³R¹⁴, —(CH₂)nOZ, or —(CH₂)nW, or X¹ and Y¹, X² and Y², or X³and Y³ are joined to form (—CO)₂O or (—CO)₂NR¹⁵ wherein R¹¹, R¹², R¹³,R¹⁴ and R¹⁵ each independently represent a hydrogen atom or ahydrocarbon group containing 1 to 20 carbon atoms, Z represents ahydrocarbon group or a hydrocarbon group substituted by a halogen atom,and W represents SiR¹⁶ _(p)D_(3-p) (wherein R¹⁶ represents a hydrocarbongroup containing 1 to 10 carbon atoms, D represents a halogen atom,—OCOR¹⁶ or —OR¹⁶, and p represents an integer of 0 to 3). n representsan integer of 0 to 10.

Norbornene addition (co)polymers are disclosed in JPA-H10-7732,JPA2002-504184, US2004/229157A1 or WO2004/070463A1 or the like. They areobtained by addition polymerization of norbornene polycyclic unsaturatedcompounds. Alternatively, they are obtained by addition polymerizationof a norbornene polycyclic unsaturated compound with ethylene,propylene, butene; or a conjugated diene such as butadiene or isoprene;or a non-conjugated diene such as ethylidene norbornene. Such norborneneaddition (co)polymers are commercially available from Mitsui Chemicals,inc. under the brand name APEL, including grades of different glasstransition temperatures (Tg) such as APL8008T (Tg 70° C.), APL6013T (Tg125° C.) or APL6015T (Tg 145° C.). Pellets are commercially availablefrom Polyplastics Co., Ltd. under the brand names TOPAS 8007, 5013,6013, 6015 and the like.

Another commercial product is Appear 3000 available from Ferrania.

Norbornene polymer hydrides can be prepared by addition polymerizationor ring-opening metathesis polymerization of polycyclic unsaturatedcompounds followed by hydrogenation as disclosed in JPA-H1-240517,JPA-H7-196736, JPA-S60-26024, JPA-S62-19801, JPA2003-1159767 orJPA2004-309979 or the like.

In the formulae above, R⁵ to R⁶ preferably represent a hydrogen atom or—CH₃, X³ and Y³ preferably represent a hydrogen atom, and the othergroups are appropriately selected. Such norbornene resins arecommercially available from JSR Corporation under the brand name Arton Gor Arton F, and also from Zeon Corporation under the brand names ZEONORZF14 and ZF16, and ZEONEX 250, 280 and 480R, and these products can beused.

The amount of the binder is preferably 30 to 80% by mass, morepreferably 40 to 60% by mass based on the total solids of the adhesivecomposition.

<<Polymerizable Monomer>>

In the present invention, any polymerizable monomers can be used in theadhesive composition (therefore, the adhesive layer). The polymerizablemonomer here contains a polymerizable group. The polymerizable group isa group that can be polymerized typically by irradiation with activerays or radiation or by the action of free radicals or an acid.

It should be noted that the polymerizable monomer is a compounddistinguished from the binder described above. The polymerizable monomeris typically a low molecular weight compound, preferably a low molecularweight compound having a molecular weight of 2000 or less, morepreferably a low molecular weight compound having a molecular weight of1500 or less, even more preferably a low molecular weight compoundhaving a molecular weight of 900 or less. Typically, the low molecularweight compound has a molecular weight of 100 or more.

The polymerizable monomers may be used in combination of several kindsas required.

Preferably, the polymerizable group is, for example, a functional groupcapable of participating in an addition polymerization reaction, andsuch functional groups capable of participating in an additionpolymerization reaction include ethylenically unsaturatedbond-containing groups, amino, epoxy and the like. The polymerizablegroup may also be a functional group capable of generating free radicalswhen photoirradiated, and such polymerizable groups include, forexample, thiol, halogens and the like. Among others, preferredpolymerizable groups are ethylenically unsaturated bond-containinggroups. Ethylenically unsaturated bond-containing groups preferablyinclude styryl, (meth)acryloyl, and allyl.

Reactive compounds containing a polymerizable group specifically include(B1) radically polymerizable compounds and (B2) ionically polymerizablecompounds.

Radically polymerizable compounds include (B11) (meth)acrylamidecompounds containing 3 to 35 carbon atoms, (B12) (meth)acrylatecompounds containing 4 to 35 carbon atoms, (B13) aromatic vinylcompounds containing 6 to 35 carbon atoms, (B14) vinyl ether compoundscontaining 3 to 20 carbon atoms, and (B15) other radically polymerizablecompounds and the like. The radically polymerizable compounds (B1) maybe used alone or as a combination of two or more of them.

Further, polymerization inhibitors such as hydroquinones, methyl etherhydroquinones and the like may also be used, as appropriate.

(Meth)acrylamide compounds containing 3 to 35 carbon atoms (B11)include, for example, (meth)acrylamide, N-methyl (meth)acrylamide,N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl(meth)acrylamide, N-tert-butyl (meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl (meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl(meth)acrylamide and (meth)acryloylmorpholine.

(Meth)acrylate compounds containing 4 to 35 carbon atoms (B12) include,for example, the monofunctional to hexafunctional (meth)acrylatesmentioned below.

Monofunctional (meth)acrylates include ethyl (meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate,isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate,stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl(meth)acrylate, 4-n-butylcyclohexl (meth)acrylate, bornyl(meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate,2-ethylhexyl diglycol (meth)acrylate, butoxyethyl (meth)acrylate,2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl(meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate,methoxypropylene monoacrylate, 3-methoxybutyl (meth)acrylate,alkoxymethyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate,alkoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate,2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl(meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl(meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl(meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl(meth)acrylate, phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate,glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate,glycidyloxypropyl (meth)acrylate, diethylene glycol monovinyl ethermonoacrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyalkyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, diethylaminopropyl (meth)acrylate, trimethoxysilylpropyl(meth)acrylate, trimethoxysilylpropyl (meth)acrylate,trimethylsilylpropyl (meth)acrylate, poly(ethylene oxide) monomethylether (meth)acrylate, oligo(ethylene oxide) monomethyl ether(meth)acrylate, poly(ethylene oxide) (meth)acrylate, oligo(ethyleneoxide) (meth)acrylate, oligo(ethylene oxide) monoalkyl ether(meth)acrylate, poly(ethylene oxide) monoalkyl ether (meth)acrylate,dipropylene glycol (meth)acrylate, poly(propylene oxide) monoalkyl ether(meth)acrylate, oligo(propylene oxide) monoalkyl ether (meth)acrylate,2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyhexahydrophthalicacid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethyleneglycol (meth)acrylate, trifluoroethyl (meth)acrylate,perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, EO-modified phenol (meth)acrylate, EO-modified cresol(meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modifiednonylphenol (meth)acrylate and EO-modified 2-ethylhexyl (meth)acrylateand the like. As used hereinbefore and hereinafter, EO means ethyleneoxide, and PO means propylene oxide.

Bifunctional (meth)acrylates include 1,4-butane di(meth)acrylate,1,6-hexane diacrylate, polypropylene diacrylate, 1,6-hexanedioldi(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyldiacrylate, neopentyl glycol di(meth)acrylate,2,4-dimethyl-1,5-pentanediol di(meth)acrylate, butylethylpropanediol(meth)acrylate, ethoxylated cyclohexanemethanol di(meth)acrylate,polyethylene glycol di(meth)acrylate, oligoethylene glycoldi(meth)acrylate, ethylene glycol di(meth)acrylate,2-ethyl-2-butylbutanedioldi(meth)acrylate, neopentyl glycolhydroxypivalate di(meth)acrylate, EO-modified bisphenol Adi(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropyleneglycol di(meth)acrylate, oligopropylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 2-ethyl-2-butyl propanedioldi(meth)acrylate, 1,9-nonane di(meth)acrylate, propoxylated ethoxylatedbisphenol A di(meth)acrylate and tricyclodecane di(meth)acrylate and thelike.

Trifunctional (meth)acrylates include trimethylolpropanetri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene oxidemodified tri(meth)acrylate of trimethylolpropane, pentaerythritoltri(meth)acrylate, dipentaerythritol tri(meth)acrylate,trimethylolpropane tri((meth)acryloyloxypropyl) ether, alkylene oxidemodified isocyanurate tri(meth)acrylate, dipentaerythritol propionatetri(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate,hydroxypivalaldehyde modified dimethylolpropane tri(meth)acrylate,sorbitol tri(meth)acrylate, propoxylated trimethylolpropanetri(meth)acrylate and ethoxylated glycerol triacrylate and the like.

Tetrafunctional (meth)acrylates include pentaerythritoltetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol propionate tetra(meth)acrylateand ethoxylated pentaerythritol tetra(meth)acrylate and the like.

Pentafunctional (meth)acrylates include sorbitol penta(meth)acrylate anddipentaerythritol penta(meth)acrylate.

Hexafunctional (meth)acrylates include dipentaerythritolhexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modifiedhexa(meth)acrylate of phosphazene and caprolactone modifieddipentaerythritol hexa(meth)acrylate and the like.

Aromatic vinyl compounds containing 6 to 35 carbon atoms (B13) includevinylthiophene, vinylfuran, vinylpyridine, styrene, methylstyrene,trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene,methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene,bromostyrene, methyl vinylbenzoate ester, 3-methylstyrene,4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene,4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene,4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene,4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene,butenylstyrene, octenylstyrene, 4-tert-butoxycarbonylstyrene,4-methoxystyrene and 4-tert-butoxystyrene and the like.

Vinyl ether compounds containing 3 to 35 carbon atoms (B14) include, forexample, the following monofunctional or polyfunctional vinyl ethers.

Monofunctional vinyl ethers include, for example, methyl vinyl ether,ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butylvinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinylether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether,4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether,dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether,methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinylether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether,methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether,2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutylvinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethyleneglycol monovinyl ether, polyethylene glycol vinyl ether, chloroethylvinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether,phenylethyl vinyl ether and phenoxypolyethylene glycol vinyl ether.

Polyfunctional vinyl ethers include, for example, divinyl ethers such asethylene glycol divinyl ether, diethylene glycol divinyl ether,polyethylene glycol divinyl ether, propylene glycol divinyl ether,butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol Aalkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl etherand the like; trimethylolethane trivinyl ether, trimethylolpropanetrivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinylether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinylether, dipentaerythritol hexavinyl ether, ethylene oxide modifiedtrimethylolpropane trivinyl ether, propylene oxide modifiedtrimethylolpropane trivinyl ether, ethylene oxide modifiedditrimethylolpropane tetravinyl ether, propylene oxide modifiedditrimethylolpropane tetravinyl ether, ethylene oxide modifiedpentaerythritol tetravinyl ether, propylene oxide modifiedpentaerythritol tetravinyl ether, ethylene oxide modifieddipentaerythritol hexavinyl ether and propylene oxide modifieddipentaerythritol hexavinyl ether.

Other radically polymerizable compounds (B15) include vinyl estercompounds (vinyl acetate, vinyl propionate and vinyl versatate and thelike), allyl ester compounds (allyl acetate and the like),halogen-containing monomers (vinylidene chloride and vinyl chloride andthe like) and olefin compounds (ethylene and propylene and the like) andthe like.

Among them, (meth)acrylamide compounds (B11) and (meth)acrylatecompounds (B12) are preferred, especially preferably (meth)acrylatecompounds (B12) because of the rate of polymerization.

Ionically polymerizable compounds (B2) include (B21) epoxy compoundscontaining 3 to 20 carbon atoms and (B22) oxetane compounds containing 4to 20 carbon atoms and the like.

Epoxy compounds containing 3 to 20 carbon atoms (B21) include, forexample, the following monofunctional or polyfunctional epoxy compounds.

Monofunctional epoxy compounds include, for example, phenyl glycidylether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether,2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide,1,3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin,1,2-epoxydecane, styrene oxide, cyclohexene oxide,3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexeneoxide and 3-vinylcyclohexene oxide.

Polyfunctional epoxy compounds include, for example, bisphenol Adiglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidylether, brominated bisphenol A diglycidyl ether, brominated bisphenol Fdiglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolacresins, hydrogenated bisphenol A diglycidyl ether, hydrogenatedbisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether,3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate,2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-di oxane,bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide,4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether,ethylenebis(3,4-epoxycyclohexane carboxylate), dioctylepoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate,1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,glycerol triglycidyl ether, trimethylolpropane triglycidyl ether,polyethylene glycol diglycidyl ether, polypropylene glycol diglycidylethers, 1,1,3-tetradecadiene dioxide, limonene dioxide,1,2,7,8-diepoxyoctane and 1,2,5,6-diepoxycyclooctane.

Among these epoxy compounds, aromatic epoxides and alicyclic epoxidesare preferred, especially preferably alicyclic epoxides because of thehigh rate of polymerization.

Oxetane compounds containing 4 to 20 carbon atoms (B22) includecompounds containing 1 to 6 oxetane rings and the like.

Compounds containing one oxetane ring include, for example,3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane,(3-ethyl-3-oxetanylmethoxy)methylbenzene,4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene,4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene,[1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl(3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethyleneglycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl(3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl) ether, tribromophenyl(3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl(3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl)ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether,pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl(3-ethyl-3-oxetanylmethyl) ether.

Compounds containing 2 to 6 oxetane rings include, for example,3,7-bis(3-oxetanyl)-5-oxanonane,3,3′-(1,3-(2-methylenyl)propanediylbis(oxymethylene))bis(3-ethyloxetane),1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane,1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycolbis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycolbis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropanetris(3-ethyl-3-oxetanylmethyl) ether,1,4-bis(3-ethyl-3-oxetanylmethoxy)butane,1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritoltris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycolbis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritolhexakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritolpentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone modifieddipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, caprolactonemodified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether,ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether,EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modifiedbisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modifiedhydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether,PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) etherand EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

The amount of the polymerizable monomer contained is preferably 5 to 75%by mass, more preferably 10 to 70% by mass, even more preferably 10 to60% by mass based on the total solids of the adhesive layer to achievegood bond strength and releasability.

Further, the ratio between the contents of the polymerizable monomer andthe binder (mass ratio) is preferably 90/10 to 10/90, more preferably20/80 to 80/20.

<<Solvent>>

Any known solvents that can form the adhesive layer can be used withoutlimitation, including N-methyl-2-pyrrolidone, 2-butanone, methyl amylketone, limonene, PGMEA (1-methoxy-2-propyl acetate) and the like,preferably N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone,limonene, or PGMEA (1-methoxy-2-propyl acetate).

The solvents are preferably used in such an amount that the solidscontent of the adhesive composition is 5 to 40% by mass.

The solvents may be used in combination of several kinds as required.

<<Photoinitiator>>

The adhesive composition (therefore, the adhesive layer) preferablycontains a photoinitiator, i.e., a compound capable of generating freeradicals or an acid when irradiated with active rays or radiation.

The presence of a photoinitiator allows the adhesive composition to becured by free radicals or an acid when the adhesive layer isphotoirradiated, whereby adhesiveness in the photoirradiated regiondecreases. If the surface of the adhesive layer is irradiated through aphotomask, for example, it would have the advantage that regions ofdifferent bond strengths can be easily prepared according to the patternof the photomask.Compounds capable of generating free radicals or an acid when irradiatedwith active rays or radiation that can be used include, for example,those known as photoinitiators described below.

The photoinitiator is not specifically limited so far as it has theability to initiate a polymerization reaction (crosslinking reaction) ina high molecular weight compound containing a polymerizable groupserving as the binder or in a reactive compound containing apolymerizable group serving as the polymerizable monomer, and it can beappropriately selected from known photoinitiators. For example, it ispreferably sensitive to radiations from UV to visible regions. Further,it may be an activator capable of producing a reaction with aphotoexcited sensitizer to generate active free radicals or an initiatorcapable of initiating cationic polymerization by generating an aciddepending on the type of the monomer.

Further, the photoinitiator preferably contains at least one compoundhaving a molar absorption coefficient of at least about 50 in the rangeof about 300 nm to 800 nm (preferably 330 nm to 500 nm).

Any of those known compounds can be used as the photoinitiator withoutlimitation, including, for example, halogenated hydrocarbon derivatives(e.g., those containing a triazine skeleton, those containing anoxadiazole skeleton, those containing a trihalomethyl group, and thelike), acyl phosphine compounds such as acyl phosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organicperoxides, thio compounds, ketone compounds, aromatic onium salts,ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azocompounds, azide compounds, metallocene compounds, organoboroncompounds, iron-arene complexes and the like.

The halogenated hydrocarbon compounds containing a triazine skeletoninclude, for example, the compounds described in Bull. Chem. Soc. Japan,42, 2924 (1969) by Wakabayashi et al.; the compounds described in GB1388492 (A); the compounds described in JP-A-S53-133428; the compoundsdescribed in DE 3337024 A1; the compounds described in J. Org. Chem.,29, 1527 (1964) by F. C. Schaefer et al.; the compounds described inJP-A-S62-58241; the compounds described in JP-A-H5-281728; the compoundsdescribed in JP-A-H5-34920; the compounds described in U.S. Pat. No.4,212,976 and the like.

The compounds described in U.S. Pat. No. 4,212,976 include, for example,compounds containing an oxadiazole skeleton (e.g.,2-trichloromethyl-5-phenyl-1,3,4-oxadiazole,2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole,2-tribromomethyl-5-phenyl-1,3,4-oxadiazole,2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole,2-trichloromethyl-5-styryl-1,3,4-oxadiazole,2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole,2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole,2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole,2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.), and the like.

Photoinitiators other than those described above include acridinederivatives (e.g., 9-phenylacridine, 1,7-bis(9,9′-acridinyl)heptane,etc.), N-phenylglycine and the like, polyhalogen compounds (e.g., carbontetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethylketone, etc.), coumarins (e.g.,3-(2-benzofuranoyl)-7-diethylaminocoumarin,3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin,3-benzoyl-7-diethylaminocoumarin,3-(2-methoxybenzoyl)-7-diethylaminocoumarin,3-(4-dimethylaminobenzoyl)-7-diethylaminocoumarin,3,3′-carbonylbis(5,7-di-n-propoxycoumarin),3,3′-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin,3-(2-furoyl)-7-diethylaminocoumarin,3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin,7-methoxy-3-(3-pyridylcarbonyl)coumarin,3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, thecoumarin compounds described in JP-A-H5-19475, JP-A-H7-271028,JP-A2002-363206, JP-A2002-363207, JP-A2002-363208, JP-A2002-363209 andthe like, etc.), acyl phosphine oxides (e.g.,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide,Lucirin TPO, etc.), metallocenes (e.g.,bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, (η5-cyclopentadienyl) (η6-cumenyl)iron (1+)hexafluorophosphate (1−), etc.), and the compounds described inJP-A-S53-133428, JP-B-S57-1819, JP-B-S57-6096 and U.S. Pat. No.3,615,455, and the like.

The ketone compounds include, for example, benzophenone,2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone,4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone,4-bromobenzophenone, 2-carboxybenzophenone,2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or itstetramethyl ester, 4,4′-bis(dialkylamino)benzophenones (e.g.,4,4′-bis(dimethylamino)benzophenone,4,4′-bis(dicyclohexylamino)benzophenone,4,4′-bis(diethylamino)benzophenone,4,4′-bis(dihydroxyethylamino)benzophenone,4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, and4-dimethylaminobenzophenone), 4-dimethylaminoacetophenone, benzil,anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone,phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone,2,4-diethylthioxanthone, fluorenone,2-benzyldimethylamino-1-(4-morpholinophenyl)-1-butanone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone,2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomers, benzoin,benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoinpropyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzildimethyl ketal), acridone, chloroacridone, N-methylacridone,N-butylacridone, N-butylchloroacridone, etc.

Other photoinitiators that can be suitably used includehydroxyacetophenone compounds, aminoacetophenone compounds, andacylphosphine compounds. More specifically, the aminoacetophenoneinitiators described in JP-A-H10-291969 and the acylphosphine oxideinitiators described in Japanese Patent No. 4225898 can also be used,for example.

Hydroxyacetophenone initiators that can be used include IRGACURE-184,DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all brandnames from BASF). Aminoacetophenone initiators that can be used includecommercially available products IRGACURE-907, IRGACURE-369, andIRGACURE-379 (all brand names from BASF). Other aminoacetophenoneinitiators that can be used include the compounds having an absorptionwavelength matched to a source of long wave radiation such as 365 nm or405 nm described in JP-A2009-191179. Acylphosphine initiators that canbe used include commercially available products IRGACURE-819 andDAROCUR-TPO (both brand names from BASF).

Photoinitiators more preferably include oxime compounds. Specificexamples of oxime initiators that can be used include the compoundsdescribed in JP-A2001-233842, the compounds described in JP-A2000-80068,and the compounds described in JP-A2006-342166.

Oxime compounds such as oxime derivatives suitably used asphotoinitiators in the present invention include, for example,3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one,3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one,2-acetoxyimino-1-phenylpropan-1-one,2-benzoyloxyimino-1-phenylpropan-1-one,3-(4-toluenesulfonyloxy)iminobutan-2-one, and2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Oxime ester compounds include the compounds described in J. C. S. PerkinII (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journalof Photopolymer Science and Technology (1995) pp. 202-232 andJP-A2000-66385; the compounds described in JP-A2000-80068,JP-A2004-534797, and JP-A2006-342166 and the like.

Commercially available products such as IRGACURE-OXE01 (from BASF) andIRGACURE-OXE02 (from BASF) can also be suitably used.

Oxime ester compounds other than those described above that may be usedinclude the compounds containing an oxime moiety substituted on thenitrogen atom of a carbazole described in JP-A2009-519904; the compoundscontaining a hetero substituent on the benzophenone moiety described inU.S. Pat. No. 7,626,957; the compounds containing a nitro group on thedye moiety described in JP-A2010-15025 and US Patent ApplicationPublication No. 2009/292039; the ketoxime compounds described inWO2009/131189; the compounds containing a triazine skeleton and an oximeskeleton in the same molecule described in U.S. Pat. No. 7,556,910; thecompounds having a maximum absorption at 405 nm and also having goodsensitivity to g-line sources described in JP-A2009-221114; and thelike.

Preferably, the cyclic oxime compounds described in JP-A2007-231000 andJP-A2007-322744 can also be suitably used. Among cyclic oxime compounds,the cyclic oxime compounds annulated with a carbazole dye described inJP-A2010-32985 and JP-A2010-185072 are especially preferred because ofhigh absorptivity leading to high sensitivity.

Further, the oxime compounds containing an unsaturated bond at aspecific site described in JP-A2009-242469 can also be suitably usedbecause they can regenerate active free radicals frompolymerization-inactive free radicals to achieve high sensitivity.

Most preferred are the oxime compounds containing a specific substituentshown in JP-A2007-269779 and the oxime compounds containing a thioarylgroup shown in JP-A2009-191061.

The molar absorption coefficient of a compound can be determined byknown methods, and specifically, it is preferably determined at aconcentration of 0.01 g/L in ethyl acetate as a solvent by using anultraviolet-visible spectrophotometer (Carry-5 spectrophotometer fromVarian), for example.

The photoinitiators used in the present invention may be used as acombination of two or more of them, if desired. The amount of thephotoinitiators contained in the adhesive composition used in thepresent invention is preferably 0.01 to 50% by mass, more preferably 0.1to 20% by mass, most preferably 0.5 to 10% by mass based on the totalsolids of the adhesive composition.

<<Thermal Polymerization Initiator>>

Preferably, the adhesive composition (therefore, the adhesive layer) ofthe present invention also contains a thermal polymerization initiator,i.e., a compound capable of generating free radicals or an acid whenheated.

Especially when it comprises a high molecular weight compound containinga polymerizable group as the binder or the polymerizable monomer, itpreferably contains a thermal polymerization initiator.

The presence of a thermal polymerization initiator has the advantagethat a more heat resistant and chemical resistant bond can be formed byheating the adhesive layer at or higher than the decompositiontemperature of the thermal polymerization initiator to cure it after theadhesive layer and the release layer have been bonded.

<<<Compounds Capable of Generating Free Radicals when Heated>>>

Compounds capable of generating free radicals when heated (hereinafteralso simply referred to as “thermal free radical generator”) that can beused include known thermal free radical generators.

The thermal free radical generator is a compound capable of generatingfree radicals by thermal energy to initiate or promote a polymerizationreaction of a high molecular weight compound containing a polymerizablegroup and a polymerizable monomer. If an adhesive layer formed by usingan adhesive composition containing a thermal free radical generator isirradiated with heat and then a workpiece and an adhesive support aretemporarily bonded, a crosslinking reaction proceeds by heat in areactive compound containing a crosslinkable group, whereby theadhesiveness (i.e., stickiness and tackiness) of the adhesive layer canbe decreased in advance as described later.

If a workpiece and an adhesive support are temporarily bonded and thenthe adhesive layer in the adhesive support is irradiated with heat, onthe other hand, a crosslinking reaction proceeds by heat in a reactivecompound containing a crosslinkable group, whereby the adhesive layer isstrengthened enough to prevent the adhesive layer from cohesive failurethat would be likely to occur during a mechanical or chemical process ofthe workpiece. Thus, the adhesiveness of the adhesive layer can beimproved.

Preferred thermal free radical generators include the compounds capableof generating an acid or free radicals when irradiated with active raysor radiation described above, among which compounds having a thermaldecomposition point in the range of 130° C. to 250° C., preferably 150°C. to 220° C. can be preferably used.

Thermal free radical generators include aromatic ketones, onium saltcompounds, organic peroxides, thio compounds, hexaaryl biimidazolecompounds, ketoxime ester compounds, borate compounds, aziniumcompounds, metallocene compounds, active ester compounds, compoundscontaining a carbon-halogen bond, azo compounds and the like. Amongothers, more preferred are organic peroxides or azo compounds,especially preferably organic peroxides.

Specifically, the compounds described in paragraphs 0074 to 0118 ofJPA2008-63554 are included.

Preferably, the adhesive layer comprises a binder, a polymerizablemonomer, and at least one of a photoinitiator and a thermalpolymerization initiator, more preferably a photoinitiator.

When the adhesive composition (therefore, the adhesive layer) accordingto the present invention further comprises a radically polymerizablemonomer especially in combination with a photoinitiator or a thermalpolymerization initiator, the adhesive layer 11 can be an adhesive layerhaving adhesiveness that decreases by irradiation with active rays orradiation or heat. In this case, the adhesive layer can be specificallya layer having adhesiveness before it is irradiated with active rays orradiation or heat but the adhesiveness decreases or is lost in regionsirradiated with active rays or radiation or heat.

<<<Compounds Capable of Generating an Acid when Heated>>>

Compounds capable of generating an acid when heated (hereinafter alsosimply referred to as “thermal acid generators”) that can be usedinclude known thermal acid generators.

Thermal acid generators preferably include compounds having a thermaldecomposition point in the range of 130° C. to 250° C., more preferably150° C. to 220° C.

Thermal acid generators include, for example, compounds capable ofgenerating an acid with low nucleophilicity when heated, such as asulfonic acid, a carboxylic acid or a disulfonyl imide.

The acid generated from the thermal acid generators is preferably astrong acid having a pKa of 2 or more such as a sulfonic acid, an alkylor aryl carboxylic acid substituted by an electron-withdrawing group, adisulfonyl imide also substituted by an electron-withdrawing group orthe like. The electron-withdrawing group includes a halogen atom such asfluorine atom, a haloalkyl group such as trifluoromethyl, nitro, orcyano.

Thermal acid generators that can be applied include photoinduced acidgenerators capable of generating an acid when irradiated with activerays or radiation. For example, they include onium salts such assulfonium salts and iodonium salts; N-hydroxyimide sulfonate compounds,oxime sulfonates, o-nitrobenzyl sulfonate and the like.

Further, sulfonic acid esters substantially incapable of generating anacid when irradiated with active rays or radiation but capable ofgenerating an acid when heated are also preferably used in the presentinvention.

A compound substantially incapable of generating an acid when irradiatedwith active rays or radiation can be identified by infrared (IR)absorption spectrometry or nuclear magnetic resonance (NMR)spectrometry, which detects no spectral change before and after thecompound is exposed.

The sulfonic acid esters preferably have a molecular weight of 230 to1,000, more preferably 230 to 800.

Sulfonic acid esters that can be used in the present invention arecommercially available or synthesized by known methods. The sulfonicacid esters can be synthesized by, for example, reacting a sulfonylchloride or a sulfonic anhydride with an appropriate polyhydric alcoholunder basic conditions.

The thermal acid generators may be used alone or as a combination of twoor more of them.

The amount of the thermal polymerization initiator contained in theadhesive composition of the present invention is preferably 0.01 to 50%by mass, more preferably 0.1 to 20% by mass, most preferably 0.5 to 10%by mass based on the total solids of the adhesive composition in orderthat the adhesiveness of the adhesive layer can be reduced when it isirradiated with heat before a member to be processed and an adhesivesupport are temporarily bonded while the adhesiveness of the adhesivelayer can be improved when it is irradiated with heat after a member tobe processed and an adhesive support have been temporarily bonded.

<<Other Components>>

In addition to the components described above, the adhesive composition(therefore, the adhesive layer) may further contain various compoundsdepending on the purposes so far as the advantages of the presentinvention are not adversely affected.

For example, sensitizing dyes, chain transfer agents, polymerizationinhibitors, and surfactants can be preferably used.

Specific examples and preferred examples of surfactants that may becontained in the adhesive composition (therefore, the adhesive layer)are the same as the surfactants that may be contained in the releaselayer composition described above.

In the present invention, the adhesive composition preferably comprisesa binder, a polymerizable monomer, a photoinitiator and a thermalpolymerization initiator.

The adhesive composition according to the present invention may containa rubber. As used herein, the “rubber” means to include any naturalrubbers and synthetic rubbers as well as elastomers. Silicone rubbersmay also be used.

Preferably, such a rubber is preferably contained at 4 to 20% by mass,more preferably 10 to 18% by mass, even more preferably 14 to 17% bymass based on the total solids of the adhesive composition.

More preferably, the rubber contains repeat monomer units of ethyleneand propylene. The amount of the ethylene monomer in the rubber ispreferably 40 to 70% by mass, more preferably 40 to 60% by mass, evenmore preferably 40 to 50% by mass when the total weight of the rubber is100% by mass. The amount of the propylene monomer in the rubber ispreferably 35 to 65% by mass, more preferably 35 to 55% by mass, evenmore preferably 35 to 45% by mass when the total weight of the rubber is100% by mass.

Still more preferably, the rubber further contains a small amount of anon-conjugated diene (e.g., an ethylidene norbornene monomer). Theamount of the non-conjugated diene in the rubber is preferably 1 to 10%by mass, more preferably 2 to 6% by mass, even more preferably 2 to 3%by mass when the total weight of the rubber is 100% by mass.

Especially preferred rubbers are ethylene-propylene-diene monomers orethylene-propylene terpolymers called EPDMs. Ethylene-propyleneterpolymers are commercially available under the brand name BUNA(registered trademark) EP from Lanxess.

A silicone rubber that can be used includes a material available fromWACKER, Burghausen under the brand name ELASTOSIL LR 3070 having a ShoreA hardness of 50.

Further, the rubber may be used as a mixture with a dissolvedhydrocarbon resin. The hydrocarbon resin is preferably contained at 65to 95% by mass, more preferably 75 to 95% by mass, even more preferably80 to 90% by mass based on the total solids.

The hydrocarbon resin to be mixed with the rubber can be selected fromthe group consisting of terpene rosins, gum rosins, wood rosins, andmixtures thereof. Preferred hydrocarbon resins are commerciallyavailable under the brand name Eastotac from Eastman Chemical Company.

The polysiloxane polymers described in paragraphs 0013 to 0015 ofJPA2013-048215 or the silphenylene-containing compounds described inparagraphs 0021 to 0027 of the same document may also be used.

<Methods for Manufacturing Semiconductor Devices>

Next, adhesive supports using the temporary bonding laminates for usedin a manufacture of semiconductor devices according to the presentinvention described above and processes for manufacturing semiconductordevices (hereinafter also referred to as “methods for manufacturingsemiconductor devices according to the present invention”) are explainedbelow.

The methods for manufacturing semiconductor devices according to thepresent invention comprise bonding a first surface of a member to beprocessed and a substrate via a temporary bonding laminate for used in amanufacture of semiconductor devices according to the present invention;subjecting the member to be processed to a heat treatment having amaximum attainable temperature in the range of 180° C. to 370° C. togive a processed member; and debonding the processed member from thebonding layer laminate; characterized in that the release layer 5% massreduction temperature higher than the maximum attainable temperature inthe heat treatment when measured in a nitrogen gas stream under theheating conditions of a constant heating rate of 20° C./min.

Each step is explained below.

The methods for manufacturing semiconductor devices according to thepresent invention comprise performing a heat treatment. The performing aheat treatment is not specifically limited so far as it is a stepcomprising heating in a manufacturing process of a semiconductor device,but preferably e.g., a step comprising heating a thinned siliconsubstrate supported on an adhesive support, more preferably a stepcomprising a heat treatment during the formation of through-siliconvias.

The performing a heat treatment in the methods for manufacturingsemiconductor devices according to the present invention is a stepcomprising a heat treatment having a maximum attainable temperature inthe range of 180° C. to 370° C., preferably a step comprising a heattreatment having a maximum attainable temperature in the range of 180 to250° C. The softening point of the first release layer is preferablyhigher than the maximum attainable temperature in the heat treatment by10 to 50° C., more preferably 20 to 50° C. When it is in such ranges,the advantages. of the present invention are achieved more effectively.The heat treatment preferably comprises heating at the maximumattainable temperature for 30 seconds to 30 minutes, more preferablyheating at the maximum attainable temperature for 1 minute to 10minutes.

Further, the methods processes preferably also comprise irradiating theadhesive layer of the temporary bonding laminate with active rays orradiation or heat before bonding the first surface of the member to beprocessed and the substrate via the temporary bonding laminate.

Further, the methods preferably also comprise removing the temporarybonding laminate remaining on the processed member using a strippingsolvent after debonding the processed member from the temporary bondinglaminate.

In the methods for manufacturing semiconductor devices according to thepresent invention, the stripping solvent preferably comprises at leastone of a hydrocarbon solvent and an ether solvent.

In the embodiment described above, the methods may further compriseremoving the adhesive layer remaining on the processed member using astripping solvent after debonding the processed member from the bondinglayers. The stripping solvent here is preferably selected from ahydrocarbon solvent and an ether solvent or a combination thereof, morepreferably selected from cyclopentane, n-hexane, cyclohexane, n-heptane,limonene, p-menthane, tetrahydrofuran (THF), 1,3-dioxolane and anisoleor a combination thereof, even more preferably comprises at least one oftetrahydrofuran, 1,3-dioxolane and anisole.

The methods for manufacturing semiconductors according to the presentinvention are explained in more detail below.

FIG. 3A, FIG. 3B and FIG. 3C are a schematic sectional view illustratinghow to temporarily bond an adhesive support and a device wafer, aschematic sectional view showing the device wafer temporarily bonded tothe adhesive support, and a schematic sectional view showing the devicewafer temporarily bonded to the adhesive support after it has beenthinned, respectively.

In an embodiment of the present invention, an adhesive support 100comprising an adhesive layer 11 on a carrier substrate 12 is firstprovided, as shown in FIG. 3A.

The carrier substrate 12 is not specifically limited to any materials,and includes, for example, a silicon substrate, a glass substrate, ametal substrate or the like, preferably a silicon substrate because itis less likely to contaminate silicon substrates typically used assubstrates for semiconductor devices and it allows the use of anelectrostatic chuck commonly used in manufacturing methods ofsemiconductor devices.The thickness of the carrier substrate 12 is, for example, in the rangeof 300 μm to 5 mm, but not specifically limited.

FIG. 4 is a schematic top view of an adhesive support according to anembodiment of the present invention.

In the embodiment of the present invention, the adhesive layer 11 in theadhesive support is formed of high adhesion regions 11A as dot regions,and low adhesion regions 11B as peripheral regions surrounding the dotregions, as shown in FIG. 4. The low adhesion regions 11B and the highadhesion regions 11A here are distributed at an approximately equaldistance over the entire surface of the adhesive layer 11 to form ahalftone pattern.

The low adhesion regions 11A and the high adhesion regions 11B areformed by pattern exposure to produce a halftone image on the adhesivelayer having adhesiveness that increases or decreases by irradiationwith active rays or radiation.

The pattern exposure to produce a halftone image is preferably performedin such a manner that the dot regions of the halftone pattern in theadhesive layer are the high adhesion regions while the peripheralregions surrounding the dot regions are the low adhesion regions.

Preferably, each dot region has an area of 0.0001 to 9 mm², morepreferably 0.1 to 4 mm², most preferably 0.01 to 2.25 mm².

The pattern exposure to produce a halftone image may be mask exposure ormaskless exposure, but preferably mask exposure through a photomask inwhich light-transmitting regions and light-shielding regions form ahalftone pattern, and in which case the area rate of the light-shieldingregions (i.e., the abundance of halftone dots on the bonding surface) ispreferably 1 to 20%, more preferably 1 to 10%, most preferably 1 to 5%in the mask because of adhesiveness and releasability.

Further, the morphology (size, shape and the like) of thelight-shielding regions corresponding to the halftone dots in thehalftone pattern of the photomask can be selected at will, and eachlight-shielding region may be in the shape of, for example, a circle,square, rectangle, diamond, triangle or star or a combination of two ormore of them of any size.

As used herein, the “low adhesion regions” refer to regions having loweradhesiveness as compared with “high adhesion regions”, and includesregions having no adhesiveness (i.e., “non-adhesive regions”).Similarly, the “high adhesion regions” refer to regions having higheradhesiveness as compared with “low adhesion regions”.

The adhesive layer 11 can be formed by applying (preferably coating) anadhesive layer composition according to the present invention in theform of a layer on the carrier substrate 12 using a known technique suchas spin coating, spray coating, roller coating, flow coating, bladecoating, dip coating or the like, and then drying it. The adhesive layermay be baked after the adhesive layer composition has been applied inthe form of a layer. The baking temperature is preferably 50 to 350° C.,more preferably 80 to 120° C. The baking time is preferably 10 secondsto 5 minutes.

The surface of the adhesive layer of the present invention comprises twoor more classes of regions having different bond strengths.

As used herein, the bond strength refers to the bond strength determinedwhen a silicon wafer is bonded to the surface of each region andsubjected to a tensile test at 250 mm/min in a direction perpendicularto the bonding surface.

The thickness of the adhesive layer 11 is, for example, in the range of1 to 500 μm, more preferably 1 to 100 μm, but not specifically limited.

The release layer can be formed by applying (preferably coating) a firstrelease layer composition and a second release layer composition in theform of a layer on a member to be processed using a known technique suchas spin coating, spray coating, roller coating, flow coating, bladecoating, dip coating or the like, and then drying them. The releaselayer may be baked after the release layer composition has been appliedin the form of a layer. Baking conditions preferably include 50 to 350°C., more preferably 60 to 200° C. The baking time is preferably 30seconds to 10 minutes. Baking may be performed in two stages, in whichcase a first stage of baking is preferably performed at a temperaturelower than a second stage of baking by about 30 to 100° C.

The thickness of the release layer is, for example, in the range of 1 to500 μm, more preferably 1 to 100 μm, but not specifically limited.

Next, temporarily bonding the adhesive support obtained as describedabove and a device wafer, thinning the device wafer, and debonding thedevice wafer from the adhesive support are explained in detail below.

As shown in FIG. 3A, a device wafer 60 (processed member) comprisesmultiple device chips 62 on a frontside 61 a of a silicon substrate 61.release layer 71 is provided on the frontside of the device wafer 60having the device chips 62. A softening point of the release layer 71 is170° C. or more.

The thickness of the silicon substrate 61 is, for example, in the rangeof 200 to 1200 μm.

Then, the surface of the release layer 71 is applied on the adhesivelayer 11 of the adhesive support 100. Thus, the surface of the firstrelease layer 71 and the adhesive layer 11 is bonded to forma temporarybonding laminate 80 comprising the first release layer 71 and theadhesive layer 11, as shown in FIG. 3B.

Then, the bonded assembly of the adhesive support 100 and the devicewafer 60 may be heated (irradiated with heat) to strengthen the adhesivelayer, if desired. This allows the adhesiveness of the adhesive support100 to be higher because it prevents the adhesive layer from cohesivefailure that would be likely to occur during a mechanical or chemicalprocess of the device wafer 60 as described later. Especially, theadhesive layer preferably contains a thermal polymerization initiatorbecause a crosslinking reaction in a reactive compound containing acrosslinkable group can be promoted by heat.

Then, the backside 61 b of the silicon substrate 61 is subjected to amechanical or chemical process, specifically a thinning process such asgrinding or chemical mechanical polishing (CMP), thereby reducing thethickness of the silicon substrate 61 (e.g., to a thickness of 1 to 200μm) to give a thinned device wafer 60′, as shown in FIG. 3C.

A further mechanical or chemical process after the thinning processcomprises forming through-holes (not shown) through the siliconsubstrate from the backside 61 b′ of the thinned device wafer andforming through-silicon vias (not shown) in the through-holes. Theprocess of forming through-silicon vias comprises performing a heattreatment having a maximum temperature lower than the softening point ofthe release layer 71. Specifically, the maximum attainable temperaturein the heat treatment is in the range of 130° C. to 370° C., preferablyin the range of 130° C. to 370° C. Maximum temperature in the heattreatment is at a temperature lower than the softening point of therelease layer.

Then, the frontside 61 a of the thinned device wafer 60′ is debondedfrom the adhesive layer 11 of the adhesive support 100.

The debonding method is not specifically limited, but preferablycomprises sliding the thinned device wafer 60′ against the adhesivesupport 100 or separating the thinned device wafer 60′ from the adhesivesupport 100. These methods allow the adhesive layer 11 and the frontside61 a of the thinned device wafer 60′ to be readily released from thetemporary bond.

After the thinned device wafer 60′ is debonded from the adhesive support100, the thinned device wafer 60′ is subjected various known processesas appropriate to prepare a semiconductor device comprising the thinneddevice wafer 60′.

In the present invention, the temporary bonding method is not limited sofar as a device wafer and a carrier substrate are bonded via a temporarybonding laminate comprising a release layer and an adhesive layer, andmay comprise preparing a temporary bonding laminate having a releaselayer on an adhesive layer in advance and bonding a carrier substrateand a device wafer to the adhesive layer and the release layer in thistemporary bonding laminate, respectively.

Further, the present invention also relates to a laminate comprising asupport such as a carrier substrate, a member to be processed such as adevice wafer, and a temporary bonding laminate provided between thesupport and the member to be processed.

Next, a conventional embodiment is explained.

FIG. 15 is a schematic sectional view illustrating how an adhesivesupport and a device wafer are released from a temporary bond accordingto a prior art.

In the conventional embodiment, an adhesive support 100′ and a devicewafer are temporarily bonded by the same procedure as explained withreference to FIG. 3A and FIG. 3B except that the adhesive support 100′comprises an adhesive layer 11′ formed of a conventional temporarybonding agent on a carrier substrate 12 as shown in FIG. 15, then thesilicon substrate in the device wafer is thinned, and then a thinneddevice wafer 60′ having the silicon substrate 61 is separated from theadhesive support 100′.

When a conventional temporary bonding agent is used, however, it isdifficult to temporarily support a member to be processed securely andreadily and to readily release a processed member from a temporarysupport without damaging the processed member. If a conventionaltemporary bonding agent having high adhesiveness is employed tosufficiently temporarily bond the device wafer and the carriersubstrate, for example, the temporary bond between the device wafer andthe carrier substrate tends to be excessively strong. If a tape (e.g., adicing tape) 70 is adhered to the backside 61 b′ of the thinned devicewafer 60′ and the thinned device wafer 60′ is separated from theadhesive support 12 to resolve this excessively strong temporary bond,as shown in FIG. 15 for example, bumps 63 drop off from device chips 62on which the bumps 63 are provided or otherwise the device chips 62 aredisadvantageously likely to be broken.

If a conventional temporary bonding agent having low adhesiveness isemployed, however, the temporary bond between the device wafer and thecarrier substrate is too weak to securely support the device wafer onthe carrier substrate.

In contrast, an adhesive layer formed of an adhesive composition of thepresent invention exhibits sufficient adhesiveness and the temporarybond between the device wafer 60 and the adhesive support 100 can bereadily resolved because the adhesive layer 11 comprises high adhesionregions and low adhesion regions. Thus, the release layer in thetemporary bonding laminate of the present invention allows the devicewafer 60 to be temporarily bonded securely and readily and the thinneddevice wafer 60′ to be readily debonded without damaging the thinneddevice wafer 60′.

The methods for manufacturing semiconductor devices according to thepresent invention are not limited to the embodiment described above, butmodifications, improvements and the like can be made as appropriate.

The shape of the halftone pattern in the adhesive layer is notspecifically limited, and an adhesive layer 21 may be formed to have ahalftone pattern comprising high adhesion regions 21A and low adhesionregions 21B wherein the high adhesion regions 21A extend outward fromthe center to form a radial pattern, as shown in the schematic top viewof FIG. 5, for example.

Alternatively, adhesive layers 22, 23, 24 may be formed to have apattern comprising high adhesion regions 22A, 23A, 24A and low adhesionregions 22B, 23B, 24B wherein the high adhesion regions 22A, 23A, 24Aextend outward from the center to form a radial pattern and have an arearate lower than the area rate of the high adhesion regions 21A in theadhesive layer 21 (see FIG. 5), as shown in the schematic top views ofFIGS. 6, 7, and 8.

Further, the size of each high adhesion region in the halftone patternis not specifically limited, and adhesive layers 25, 26, 27, 28, 29, 30comprising high adhesion regions 25A, 26A, 27A, 28A, 29A, 30A and lowadhesion regions 25B, 26B, 27B, 28B, 29B, 30B may be formed wherein thehigh adhesion regions 25A, 26A, 27A, 28A, 29A, 30A have a size changedfrom the size of the high adhesion regions 11A in the adhesive layer 11(see FIG. 4), as shown in FIG. 9, 8, 9, 10, 11, 12.

Although an adhesive layer formed of an adhesive composition of thepresent invention is provided on a carrier substrate to form an adhesivesupport before it is temporarily bonded to a device wafer in theembodiment described above, it may be first provided on a release layerto form a temporary bonding laminate, in which case the adhesive layerand the release layer in the temporary bonding laminate are bonded to acarrier substrate and a device wafer, respectively.

For example, the mask used for pattern exposure may be a binary mask ora halftone mask.

Although exposure is performed through a mask, it may be selectiveexposure using an electron beam or the like.

Further, the embodiment described above preferably further comprisesirradiating the adhesive layer of the temporary bonding laminate withactive rays or radiation or heat before bonding the first surface of themember to be processed and the substrate via the temporary bondinglaminate.

Although the adhesive layer is a monolayer structure in the embodimentdescribed above, the adhesive layer may be a multilayer structure. Anadhesive layer having a multilayer structure may be formed by coating anadhesive composition stepwise by any one of the known techniquesdescribed above before irradiation with active rays or radiation; orcoating an adhesive composition by any one of the known techniquesdescribed above after irradiation with active rays or radiation or thelike. In an embodiment comprising an adhesive layer having a multilayerstructure wherein the adhesive layer 11 is an adhesive layer havingadhesiveness that decreases by irradiation with active rays or radiationor heat, for example, the adhesiveness of the adhesive layer as a wholecan be decreased by decreasing adhesion between layers by irradiationwith active rays or radiation or heat.

Further, the member to be processed supported on the adhesive support isnot limited to a silicon substrate as mentioned in the embodimentdescribed above, but may be any member to be processed capable of beingsubjected to a mechanical or chemical process during manufacturingprocesses of semiconductor devices.

For example, the member to be processed may also be a compoundsemiconductor substrate, and specific examples of compound semiconductorsubstrates include SiC substrates, SiGe substrates, ZnS substrates, ZnSesubstrates, GaAs substrates, InP substrates, and GaN substrates and thelike.

Further, the mechanical or chemical process of the silicon substratesupported by the adhesive support is not limited to thinning of thesilicon substrate and formation of through-silicon vias as mentioned inthe embodiment described above, but may be any necessary process inmanufacturing processes of semiconductor devices.

Further, the shape, size, number, location and the like of thelight-transmitting regions and light-shielding regions in the mask, thehigh adhesion regions and low adhesion regions in the adhesive layer,and the device chips in the device wafer are not limited to the examplesshown in the embodiment described above, but may be any values so far asthe present invention can be achieved.

EXAMPLES

The following examples further illustrate the present invention, but thepresent invention is not limited to these examples and changes may bemade without departing from the spirit of the invention. Unlessotherwise specified, “parts” and “%” are based on mass.

<Formation of an Adhesive Support (Adhesive Layer (B))>

A 4-inch Si wafer was coated with each liquid adhesive compositionconsisting of the components shown in Table 1 below using a spin coater(Opticoat MS-A100 from Mikasa, 1200 rpm, 30 seconds), and then bakedunder the baking conditions described in Table 1 to form a wafer 1provided with an adhesive layer having a thickness of 10 μm (i.e., anadhesive support). Then, the adhesive layer was exposed at 2000 mJ/cm²to produce a halftone image by irradiation from the side of the adhesivelayer of the wafer 1 using a UV exposure system (LC8 from HamamatsuPhotonics K.K.) through a photomask having a halftone pattern consistingof light-transmitting regions and light-shielding regions wherein thelight-shielding regions are dot regions in the halftone pattern.Exposure was performed while the shape of each dot region(light-shielding region) of the photomask was changed as shown in Table3 in each Example (Table 3 also shows the area rate oflight-transmitting regions in each photomask). The pattern formed by dotregions (high adhesion regions) on the surface of the adhesive layer isa pattern as shown in FIG. 4.

TABLE 1 Thermal polymerization Binder Polymerizable monomerPhotoinitiator initiator Solvent Content Content Content Content ContentBaking Type (parts) Type (parts) Type (parts) Type (parts) Type (parts)conditions Adhesive Resin 50 Polymerizable 50 Photoinitiator 5 Thermal 5S1 150 100° C. composition 1 (1) monomer (1) (1) polymerization 30seconds initiator (1) Adhesive Resin 50 Polymerizable 50 Photoinitiator5 Thermal 5 S2 150 100° C. composition 2 (1) monomer (2) (1)polymerization 30 seconds initiator (1) Adhesive Resin 50 Polymerizable50 Photoinitiator 5 Thermal 5 S3 150 100° C. composition 3 (2) monomer(1) (1) polymerization 30 seconds initiator (1) Adhesive Resin 10 none —none — none — S4 100 100° C. composition 4 (3) 60 seconds Resin 50 (4)

The compounds described in Table 1 are as follows.

<Binders>

Resin (1): ESTYRENE MS200NT (an MS resin from Nippon Steel Chemical Co.,Ltd.)

Resin (2): ZEONEX 480R (a cycloolefin resin from Zeon Corporation)

Resin (3): Buna EP T6250 (an ethylene-propylene terpolymer rubber fromLANXESS)

Resin (4): Eastotac H-142W (a hydrocarbon resin from Eastman ChemicalCompany)

<Polymerizable Monomers>

Polymerizable monomer (1): A-DCP (a bifunctional acrylate fromShin-Nakamura Chemical Co., Ltd.)

Polymerizable monomer (2): A-BPE-4 (a bifunctional acrylate fromShin-Nakamura Chemical Co., Ltd.)

<Photoinitiator>

Photoinitiator (1): KAYACURE DETX-S (2,4-dimethylthioxanthone fromNippon Kayaku Co., Ltd.)

<Thermal Polymerization Initiator>

Thermal polymerization initiator (1): PERBUTYL Z (tert-butylperoxybenzoate from NOF CORPORATION)

<Solvents>

S1: Methyl amyl ketone

S2: PGMEA (propylene glycol 1-monomethyl ether 2-acetate)

S3: Limonene

S4: 1-Dodecene

<Preparation of a Member to be Processed (Release Layer (A))>

A 4-inch Si wafer provided with Cu electrodes having a height of 10 μmand a diameter of 50 μm spaced 200 μm apart on its surface was coatedwith each liquid release layer composition consisting of the componentsshown in Table 2 below on the side having these electrodes using a spincoater (Opticoat MS-A100 from Mikasa, 1200 rpm, 30 seconds), and thenbaked under the conditions described in Table 2 to form a wafer 2provided with a release layer having a thickness of 40 μm. Baking wasperformed in two stages. Specifically, a first stage of baking wasperformed at the temperature and for the time described in each upperrow in Table 2, and a second stage of baking was performed at thetemperature and for the time described in each lower row in Table 2.The softening point of the release layer was determined using theviscoelastometer Rheosol-G5000 (from UBM). Specifically, the softeningpoint of the release layer is determined as the temperature at which theloss tangent (tan δ) measured using a viscoelastometer underpredetermined heating conditions is maximum. In the Examples, it wasdetermined using the viscoelastometer Rheosol-G5000 when the temperatureof the release layer was raised from 25° C. to 500° C. at a heating rateof 5° C./min and a strain of an angle of 0.05° was applied to therelease layer at a frequency of 1 Hz.The Td of each binder and heat resistant liquid was determined by thethermogravimetric analyzer Q500 (from TA Instruments). Specifically, theTd of each heat resistant liquid was determined as the temperature atwhich the percentage of the initial mass remaining was 95% when measuredby a thermogravimetric analyzer in a nitrogen gas stream of 60 mL/rainunder the heating conditions of a constant heating rate of 20° C./min.

TABLE 2 Binders Heat resistant liquids Solvent Release layer Liquidrelease layer Content Content Content Softening Point composition Type(%) Type (%) Type (%) Baking conditions (° C.) Solution 1 Resin 20 Heatresistant liquid 0.2 Anisole 79 100° C. 5 minutes 250 (1) (1) 180° C. 10minutes Solution 2 Resin 25 Heat resistant liquid 0.1N-ethyl-2-pyrrolidone 74.5 100° C. 5 minutes 220 (2) (1) 250° C. 10minutes Solution 3 Resin 10 Heat resistant liquid  0.02N,N-dimethylacetamide 89.9 100° C. 5 minutes 300 (3) (1) 250° C. 10minutes Solution 4 Resin 25 Heat resistant liquid 0.1 Limonene 74.5 100°C. 5 minutes 150 (4) (1) 150° C. 10 minutes Solution 5 Resin 20 Heatresistant liquid 0.2 Anisole 79 100° C. 5 minutes 250 (1) (2) 180° C. 10minutes Solution 6 Resin 20 Heat resistant liquid 0.2 Anisole 79 100° C.5 minutes 250 (1) (3) 180° C. 10 minutes Solution 7 Resin 20 None —Anisole 80 100° C. 5 minutes 250 (1) 180° C. 10 minutes Solution 8 Resin20 Heat resistant liquid 0.2 Anisole 79 100° C. 5 minutes 250 (1) (4)180° C. 10 minutes Solution 9 Resin 25 Heat resistant liquid 0.1Limonene 74.9 100° C. 5 minutes 100 (5) (3) 150° C. 10 minutes Solution10 Resin 20 Heat resistant liquid 0.1 NMP 79.9 200° C. 10 minutes 470(6) (3) 300° C. 30 minutes<Binders>Resin (1): PCZ-200 (a polycarbonate resin having a Td of 270° C. fromMGC)Resin (2): Ultrason E6020 (a polyether sulfone resin having a Td of 330°C. from BASF)Resin (3): Durimide 10 (a polyimide resin having a Td of 350° C. fromFujifilm)Resin (4): Clearon P150 (a hydrocarbon resin having a Td of 200° C. fromYASUHARA CHEMICAL CO., LTD.)Resin (5): TOPAS 8007 (a hydrocarbon resin having a Td of 300° C. fromPolyplastics Co., Ltd.)Resin (6): U-Varnish-S (a polyimide resin having a Td of 550° C. fromUbe Industries, Ltd.)<Heat Resistant Liquids>Heat resistant liquid (1): UNISTER H481R (a polyester polyol having a Tdof 260° C. from NOF CORPORATION)Heat resistant liquid (2): KF-54 (a polyorganosiloxane having a Td of270° C. from Shin-Etsu Chemical Co., Ltd.)Heat resistant liquid (3): the ionic liquid A shown below (an ionicliquid having a Td of 310° C. from Nisshinbo) Ionic liquid A

Heat resistant liquid (4): Polyethylene glycol 400 (a polyethyleneglycol having a Td of 200° C. from Wako Pure Chemical Industries, Ltd.)<Preparation of Adhesion Test Specimens>

Test specimens were prepared by bonding the wafer 1 and the wafer 2 ineach combination described in Table 3 below under heat and pressure.

<<Pressure Bonding>>

A 4-inch Si wafer having no coating on the surface or a 4-inch Si waferprovided with a release layer (hereinafter referred to as wafer 2) wasdivided into sample pieces of 20 mm×30 mm. Wafer 1 was divided intosample pieces of 20 mm×30 mm in the same manner, and overlaid on thewafer having no coating on the surface or the release layer of the wafer2 in such a manner that the adhesive layer comes into contact with it ina square of 20 mm×20 mm and bonded under pressure and heat at 1 N/cm²,120° C. for 3 minutes.

<Determination of the Bond Strength of Laminate Test Specimens>

The prepared test specimens were measured for their shear bond strengthusing a tensile tester (from IMADA CO., LTD.) in a direction along theplane of the adhesive layer under the conditions of 250 mm/min. Theresults are shown in Table 3 below.

<Evaluation of the Peel Strength and Anti-Outgassing Performance of theLaminate Test Specimens>

The prepared sample pieces were evaluated for their anti-outgassingperformance by the TDS (Thermal Desorption Spectrometer) EMD-WA1000S/Wfrom ESCO Ltd. Specifically, 1-cm square samples were heated from roomtemperature to 300° C. at 20° C./min by the spectrometer in high vacuum(1×10⁻⁷ Pa), and rated as A if the degree of vacuum in the chamber ofthe spectrometer remained at 2×10⁻⁷ Pa or less until 200° C. wasreached, or rated as B if it did not. The results are shown in Table 3below.

<Evaluation of the Removal of the Bonding Layers of the Laminate TestSpecimens>

After the prepared sample pieces were separated, the wafer 2 wasimmersed in each solvent described in Table 3, and the time (minuets)required for both adhesive layer and release layer to be removed fromthe wafer 2 was determined. The results are shown in Table 3 below.

TABLE 3 Adhesive Release Abundance of Bond Peel Anti- layer layer Shapeof halftone dots strength strength out- Peeling Removal (B) (A) halftonedots (%) (N/25 mm²) (N/25 mm²) gassing solvent (minuets) ComparativeAdhesive Solution 4 Not exposure Adhesion on 50 12 B p-menthane 20Example 1 composition 1 entire surface Comparative Adhesive Solution 8Each side of 4% 50 8 B THF 15 Example 2 composition 1 square is 1 mmArea is 1 mm² Comparative Adhesive Solution 7 Not exposure 4% 50 10 A1,3-dioxolane 45 Example 3 composition 1 Adhesion on entire surfaceComparative Adhesive None Each side of 4% 50 25 A NMP >60 Example 4composition 1 square is 1 mm Wafer Area is 1 mm² cracking ComparativeNone Solution 1 — — 0 — A — Example 5 Example 1 Adhesive Solution 1 Eachside of 4% 50 2 A THF 12 composition 1 square is 1 mm Area is 1 mm²Example 2 Adhesive Solution 2 Circle diameter 3% 40 2 A NMP 20composition 2 is 1 mm Area is 0.785 mm² Example 3 Adhesive Solution 3Not exposure Adhesion on 50 10 A Dimethyl- 20 composition 3 entiresurface acetamide Example 4 Adhesive Solution 5 Each side of 4% 50 2 ANMP 20 composition 1 square is 1 mm Area is 1 mm² Example 5 AdhesiveSolution 6 Each side of 4% 50 3 A Anisole 15 composition 2 square is 1mm Area is 1 mm² Example 6 Adhesive Solution 1 Not exposure Adhesion on50 12 A THF 12 composition 4 entire surface Example 7 Adhesive Solution9 Not exposure Adhesion on 50 15 A THF 12 composition 4 entire surfaceExample 8 Adhesive Solution 10 Not exposure Adhesion on 50 8 A NMP 20composition 4 entire surface

The results above show that Comparative examples 1 and 2 using a releaselayer material having a Td of less than 250° C. exhibited insufficientanti-outgassing performance; Comparative example 3 in which the releaselayer does not contain a heat resistant liquid exhibited insufficientremovability; Comparative example 4 not comprising a release layerexhibited insufficient releasability; and Comparative example 5comprising a release layer with no adhesive layer exhibited insufficientadhesiveness. In contrast, Examples 1 to 6 were shown to achieveadhesiveness, releasability, anti-outgassing performance andremovability at the same time even after a high temperature process(more specifically at 180° C. to 370° C.) because the release layers inthe temporary bonding laminates of the present invention comprise abinder having a Td of 250° C. or more and a heat resistant liquid.

DESCRIPTION OF THE REFERENCE NUMERALS

-   11, 21 to 30, 11′: adhesive layer;-   11A, 21A to 30A: high adhesion regions;-   11B, 21B to 30B: low adhesion regions;-   12: carrier substrate;-   60: device wafer;-   60′: thinned device wafer;-   61: silicon substrate-   61 a: frontside of the silicon substrate;-   61 b: backside of the silicon substrate;-   61 b′: backside of the thinned device wafer;-   62: device chips;-   63: bumps;-   70: tape;-   1, 71: release layer;-   80: temporary bonding laminate;-   100, 100′: adhesive support.

What is claimed is:
 1. A temporary bonding laminate for use in amanufacture of semiconductor devices, comprising: (A) a release layerand (B) an adhesive layer, wherein: the release layer comprises (a1) acompound being liquid at 25° C. and having a 5% mass reductiontemperature of 250° C. or more when measured in a nitrogen gas streamunder heating conditions of a constant heating rate of 20° C./min; and(a2) a binder having a 5% mass reduction temperature of 250° C. or morewhen measured in a nitrogen gas stream under heating conditions of aconstant heating rate of 20° C./min; the compound being liquid at 25° C.is selected from the group consisting of polyol esters, diesters,polyphenyl ethers, polyethylene glycols, polypropylene glycols,long-chain carboxylic acids, and ionic liquids; and the adhesive layer(B) comprises a binder, a polymerizable monomer, and at least one of aphotoinitiator and a thermal polymerization initiator.
 2. The temporarybonding laminate for use in a manufacture of semiconductor devicesaccording to claim 1, wherein the release layer (A) has a softeningpoint of 200° C. to 450° C.
 3. The temporary bonding laminate for use ina manufacture of semiconductor devices according to claim 1, wherein thebinder (a2) is a thermoplastic resin.
 4. The temporary bonding laminatefor use in a manufacture of semiconductor devices according to claim 3,wherein the thermoplastic resin is at least one kind of thermoplasticresin selected from the group consisting of polyether sulfone resins,polyimide resins, polyester resins, polybenzimidazole resins,polyphenylene ether resins, polyphenylene sulfide resins,polyamide-imide resins and polyether ketone resins.
 5. The temporarybonding laminate for use in a manufacture of semiconductor devicesaccording to claim 1, wherein the liquid compound (a1) is contained inan amount of 0.01 to 10% by mass of the release layer.
 6. A method formanufacturing a semiconductor device, comprising: bonding a firstsurface of a member to be processed and a substrate via the temporarybonding laminate for used in a manufacture of semiconductor devicesaccording to claim 1; subjecting the member to be processed to a heattreatment having a maximum attainable temperature in a range of 180° C.to 370° C. to give a processed member; and debonding the processedmember from the bonding layer laminate; wherein the release layer has 5%mass reduction temperature higher than the maximum attainabletemperature in the heat treatment when measured in a nitrogen gas streamunder heating conditions of a constant heating rate of 20° C./min. 7.The method for manufacturing a semiconductor device according to claim6, further comprising irradiating the adhesive layer of the temporarybonding laminate with active rays or radiation or heat before bondingthe first surface of the member to be processed and the substrate viathe temporary bonding laminate.
 8. The method for manufacturing asemiconductor device according to claim 6, further comprising removingthe temporary bonding laminate remaining on the processed member with astripping solvent after debonding the processed member from thetemporary bonding laminate.
 9. The method for manufacturing asemiconductor device according to claim 8, wherein the stripping solventcomprises at least one kind of a hydrocarbon solvent and an ethersolvent.
 10. The method for manufacturing a semiconductor deviceaccording to claim 9, wherein the stripping solvent comprises at leastone kind of cyclopentane, n-hexane, cyclohexane, n-heptane, limonene,p-menthane, tetrahydrofuran (THF), 1,3-dioxolane, and anisole.
 11. Thetemporary bonding laminate for use in a manufacture of semiconductordevices according to claim 1, wherein the release layer is a singlelayer comprising both of the compound (a1) being liquid at 25° C. andthe binder (a2).
 12. The temporary bonding laminate for use in amanufacture of semiconductor devices according to claim 1, wherein thepolymerizable monomer has a molecular weight of 1,500 or less.
 13. Thetemporary bonding laminate for use in a manufacture of semiconductordevices according to claim 1, wherein the amount of the polymerizablemonomer in the adhesive layer is 10 to 70% by mass based on the totalsolids of the adhesive layer.
 14. The temporary bonding laminate for usein a manufacture of semiconductor devices according to claim 1, whereinthe mass ratio between the contents of the polymerizable monomer and thebinder is 20/80 to 80/20.
 15. A kit comprising a release layer formingcomposition and an adhesive layer forming composition, wherein: therelease layer forming composition contains (a1) a compound being liquidat 25° C. and having 5% mass reduction temperature of 250° C. or morewhen measured in a nitrogen gas stream under the heating conditions of aconstant heating rate of 20° C./min, and (a2) a binder having 5% massreduction temperature of 250° C. or more when measured in a nitrogen gasstream under the heating conditions of a constant heating rate of 20°C./min; the compound being liquid at 25° C. is selected from the groupconsisting of polyol esters, diesters, polyphenyl ethers, polyethyleneglycols, polypropylene glycols, long-chain carboxylic acids, and ionicliquids; and the adhesive layer forming composition comprises a binder,a polymerizable monomer, and at least one of a photoinitiator and athermal polymerization initiator.